Third-Liquid Phase Transfer Catalysis for Horner–Wadsworth

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Third-liquid phase transfer catalysis for Horner-Wadsworth-Emmons reactions of “moderately acidic” and “weakly acidic” phosphonates Qiangqiang Zhao, Lei YANG, and Yifeng Shen Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b01562 • Publication Date (Web): 22 Jun 2016 Downloaded from http://pubs.acs.org on June 23, 2016

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Industrial & Engineering Chemistry Research

Third-liquid phase transfer catalysis for HornerWadsworth-Emmons reactions of “moderately acidic” and “weakly acidic” phosphonates Qiangqiang Zhao†‡*; Lei Yang†‡; Yifeng Shen†‡

†Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China ‡Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China

ACS Paragon Plus Environment

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KEYWORDS: Third-liquid phase transfer catalysis; Weakly acidic substrate; Hydroxideinitiated phase transfer catalysis; Horner-Wadsworth-Emmons Reaction

ABSTRACT: Horner-Wadsworth-Emmons (HWE) reaction was investigated in green thirdliquid phase-transfer catalysis (TLPTC) system. With 6% equiv of the catalyst and 50% NaOH aqueous solution, the third phase was generated. In this TLPTC system, HWE reactions of benzaldehydes bearing electron-donating group with “weakly” or “moderately” acidic phosphonates proceeded in high yield (>90%) with all E-isomer product (stilbene). Teraoctyl ammonium bromide (TOAB) afforded a high yield of 93% for HWE reaction of benzaldehydes with electron-withdrawing groups. It was found that the ratio of E-stilbene to Z-stilbene was also influenced by the steric hindrance of the achiral quaternary ammonium salt catalyst. The isolated yield and geometric selectivity for HWE reaction kept unchanged in four consecutive runs of both the third and the aqueous phase. Highly efficient and practical hydroxide-initiated TLPTC system was developed for HWE reaction.


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1. INTRODUCTION Hydroxide-initiated phase-transfer catalysis (HI-PTC) which facilitates the use of inexpensive hydroxide base and obviates the need for dipolar aprotic solvent is one of the most synthetically useful PTC techniques, and has been applied successfully in a large number of reactions, such as alkylation of phenols, dichlorocarbene addition, carbon-alkylation and carbon-arylation of phenylacetonitrile derivates, Knoevenagel condensation reaction, Witting reaction and HornerWadsworth-Emmons (HWE) reaction.1-3 Liquid-liquid PTC (LL-PTC) system, solid-liquid PTC system, third-liquid PTC (TLPTC) system and solid-liquid-liquid system was always adopted used to conduct HI-PTC reaction.4-10 Among these PTC systems, TLPTC has been demonstrated as a powerful method against biphasic PTC in a number of commercially hydroxide-initiated reactions. The advantages of TLPTC include high reaction rate and selectivity, easy separation of the catalyst and the product, mild reaction conditions, and steady reuse of the catalyst.11,

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Although these properties make TLPTC system a promising class of new heterogeneous catalysis systems, it is generally acknowledged that the full potential of the new synthetic technique has not been identified, especially for hydroxide-initiated reaction. Previous studies on hydroxide-initiated reaction in TLPTC system were aimed at (i) Oalkylation of phenolic compounds,13, 14 (ii) alkoxylation of alcohol to produce ethers,15, 16 (iii) isomerization of allylanisole,17 (iv) dehydrobromination of phenylethyl bromide or 2bromooctane,18 and (v) dichlorocarbene reaction.19 Although, substrates in above TLPTC systems included “very acidic” (pKa90%) and geometric selectivity (>99:1) are obtained in HWE reactions of benzaldehydes bearing EWGs with each phosphonate. ii) Isolated yields for HWE reactions of benzaldehydes bearing EWGs are lower than that bearing electron-donating groups (EDGs).

Table 1 Yields and E/Z ratios of HWE reactions in TLPTC systema

94%; >99/1; 70minb

“Weakly acidic” phosphonate (DEBP)

96%; >99/1; 85min

93%; >99/1; 100min

78%; 83/17, 40min

63%; 78/22; 30min

>99/1; 30min

48%; >99/1; 30min

0; 200min

96%; >99/1; 60min

94%; >99/1; 75min

95%; >99/1; 80min

89%; 99/1; 130min

53%;

”Moderately


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Acidic” phosphonate (DECP) 91%; >99/1; 100min

88%; >99/1; 30min

79%; >99/1; 20min

66%; >99/1; 20min

0; 200min

69%; >99/1; 20min a

Reaction condition: 5 mmol of DEBP, 5.5 mmol of aldehyde, 0.3 mmol TBAB, 20 g of 50% (w/w) NaOH, 15 mL of toluene, 1200 rpm, 45 °C. bIsolated Yield; The reaction completion time was determined by HPLC analysis. iii) Geometric selectivity is varied with the substitute in the reactants. Products are all Eisomers except HWE reactions of DEBP with benzaldehydes containing ortho-chloro group. Moreover, the ratio of Z-stilbene to E-stilbene further increases, when the second chloro-group is introduced on the para-position. However, no Z-product is found in HWE reactions of DECP with any benzaldehyde. iv) The reaction rate and isolated yields for HWE reactions of the “moderately acidic” substrate (DECP) are higher than those of DEBP. Nevertheless, isolated yields for HWE reactions of benzaldehydes bearing EWGs are still less than 85%. TLPTC system affords comparable isolated yields and geometric selectivity to those in LLPTC system. Importantly, the reaction rate and isolated yield are raised with the formation of third phase. The reaction time decreases and the yield has little change for benzaldehydes bearing EDGs, whereas the yield increases and the reaction time has little change for benzaldehydes bearing EWGs. The result can be rationalized with reference to different dependences of the main reaction rate and side reaction rate on the aggregation of the catalyst (the third phase). In PTC system, the side reaction of benzaldehyde are Cannizarro reaction and competitive with HWE reaction. The side reaction of benzaldehyde, which follows the interfacial mechanism can


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be induced by a relatively weak alkaline agent. The rate-determining step is the bond-forming reaction for the side reaction of the benzaldehyde in PTC system,42 whereas is the transfer of the carbanion and the bond-forming reaction for HWE reaction. In TLPTC system, the aggregation of the catalyst only causes the enhancement of the transfer rate and generation rate of the active intermediate. In this case, the rate of HWE reaction in TLPTC system is higher than that in LLPTC system, whereas the rate of the side reaction has little change. Side reactions of benzaldehydes bearing EWGs in TLPTC system still proceed. However, the ratio of benzaldehyde in the side reaction to that in HWE reaction decreases owing to the relatively high rate of HWE reaction. A higher yield of stilbene than that in LLPTC system is obtained. For benzaldehydes bearing EDGs, because the side reaction hardly occurs in both LLPTC system and TLPTC system, only HWE reaction rate increases and the yield remains unchanged. This explanation also is certified in the following experiment. Despite of the limited volume and the unique generating process for the third phase, this TLPTC system is suitable for HWE reactions of “weakly acidic” phosphonate (DEBP) and “moderately acidic” phosphonate. 3.3. Effect of the catalyst To find efficient TLPTC system for HWE reactions of benzaldehydes bearing EWGs, five other phase-transfer catalysts and two surfactants was used viz., tetraethyl ammonium bromide (TEAB), benzyltriethyl ammonium bromide (BTEAB), methyltrioctyl ammonium bromide (TOMAB), teraoctyl ammonium bromide (TOAB), dodecyltrimethyl ammonium bromide (DTMAB), hexadecyltrimethyl ammonium bromide (HTMAB). The catalytic activities in HWE reaction of o-chlorobenzaldehyde and DEBP were compared. Geometric selectivity and isolated yields were shown in Fig. 2 and images of the reaction mixture were listed in Fig. 3.


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Fig. 2. Effect of various catalysts on geometric selectivity and the isolated yield; 5 mmol of DEBP, 5 mmol of o-chlorobenzaldehyde, 0.3 mmol of catalyst, 20 g of 50% (w/w) NaOH, 15 mL of toluene, 1200 rpm, 45°C. Error bars represent the standard deviation between replicates (n = 3). As shown in Fig.2, not only isolated yields and reaction rates but also geometric selectivity are influenced by the structure of these chiral catalysts, which are similar to those caused by K+, Na+ and Li+ in homogenous HWE system.43,

44

The isolated yield increases with the increase in

lipophilicity for the catalyst cation, whereas the ratio of E-stilbene decreases (Fig. 1). A yield of 92% was obtained with TOAB as the catalyst, whereas E/Z ratio decrease to 1:4. Furthermore, the volume of the third phase is also affected by the nature of the catalyst (Fig. 3). Only is the clear third phase found for TBAB and TOAB, while the third phase is not generated and the aqueous phase is emulsified for TEAB, BTEAB and TMAB. Interestingly, both the third phase and the emulsion are generated for surfactants (HTMAB and DTMAB).


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Fig. 3. Images of third liquid PTC system with various catalyst (standing 2h, 30°C). For exploring the effect of the side reaction, initial reaction rates of o-chlorobenzaldehyde and stilbene in these TLPTC systems were calculated. Because the side reaction and HWE reaction occur simultaneously, the initial reaction rate of benzaldehyde includes the rate of stilbene and the rate of side reaction. As shown in Fig. 4, the initial reaction rate of stilbene increased as the increase in lipophilicity of the catalyst. However, the initial reaction rate of benzaldehyde remained constant when TBAB, TOMAB and TOAB were used. For TOAB, the initial reaction rate of stilbene was equal to that of benzaldehyde, which suggested that the side reaction of ochlorobenzaldehyde could be neglected.


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Fig. 4. Effect of various catalysts on initial reaction rates for benzaldehyde and stilbene; 5 mmol of DEBP, 5 mmol of o-chlorobenzaldehyde, 0.3 mmol of catalyst, 20 g of 50% (w/w) NaOH, 15 mL of toluene, 1200 rpm, 45°C. Error bars represent the standard deviation between replicates (n = 3). Diethyl phosphate anion (PO−) which couples with the catalyst cation is found in the third phase and is an important parameter for the formation of the third phase.45 Because much ionpair cannot dissolve into the organic phase and the aqueous phase, the third phase with much ion-pair aggregated is generated. The ion-pair is hardly generated owing to the lower liphopolicity of the catalyst cation for TEAB and BTEAB. More PO− is coupled in the third phase and the ion-pair has a poor dissolubility of in this TLPTC system when more lipophilic catalyst cation is used. Meanwhile, the symmetric structure and a long chain can easily initiate the ordered arrangement of the aggregated ion-pair. Therefore, third phase is achieved for TBAB, TOAB, HTMAB and DTMAB. Isolated yields for HWE reactions are dependent on the difference between the rate of side reaction and the rate of HWE reaction46. The key factor influenced the catalytic activity for HWE reaction is lipophilicity of the catalyst and the third phase, while is lipophilicity and accessary number of the catalyst influence for the side reaction. This is because the side reaction of benzaldehyde can be induced by a relatively weak alkaline agent and follows the interfacial mechanism47. With more hydrophilic catalyst (TEAB and BTEAB), the side reaction occurs easily and has a higher rate than HWE reaction, thereby isolated yields are less than 50%. Much more carbanion ion-pair can be extracted into the organic phase with the increase in lipophilicity of the catalyst, thereby generating a higher rate for both HWE reaction and the side reaction. For TOAB and TBAB, HWE reaction rate intensively increases and is significantly higher than those


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for other catalysts with the additional effect of the third phase. Meanwhile, TOAB has a relatively low accessary parameters, resulting in the fact that the side reaction of ochlorobenzaldehyde

hardly

proceeds.

Therefore,

the

initial

reaction

rate

for

o-

chlorobenzaldehyde is equal to that for stilbene and a higher yield is obtained. Because the side reaction easily occurs, a low yield is obtained for TBAB. TOMAB has a higher accessary parameter than TOAB and TBAB, and the third phase is not generated. Consequently, the side reaction rate is as high as that of HWE reaction and the isolated yield is much lower than that for TOAB. For HTMAB and DTMAB, the accessary parameter play a more important role than lipophilicity on catalytic activity, resulting in the relatively high side reaction rate and low yield. 3.4. Geometric selectivity In HWE reaction, geometric selectivity is dependent on the conformation of four-center oxaphosphetane (OPA) which is generated in the bond-forming reaction of the carbanion with benzaldehyde. Geometric selectivity of HWE reaction under TLPTC conditions is as high as that in biphasic PTC system owing to the same bond-forming reaction. Cycloaddition transition states (TS) for OPA formation have two conformation - cis TS (puchered) and trans TS (planar), thereby generating corresponding Z-product and E-product.48 Generally, for HWE reaction, geometric selectivity is governed by 1,2 interaction. P-Cl bond and QA interaction in TS are generated and can influence geometric selectivity (Fig. 5) for HWE reaction in PTC system, because the energy gap between these two TS is varied with the substitute in benzaldehydes and catalyst cations.


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Fig. 5. Proposed TS structure model and rationale of selectivity for HWE reaction. (a): HWE reaction for all reactants; (b): HWE reaction of o-chlorobenzaldehyde with DEBP. 1,2 interaction is a steric interaction between the aldehyde substituent (Ph1) and the ylide substituent (Ph2) in cis TS. Trans TS which is less hindered is easily generated and E-stilbene is the main product. However, P-Cl bond interaction is introduced when o-chlorobenzaldehyde is used. Chloro substituent on ortho-position of benzaldehyde aryl group can bond to phosphorus and this bonding interaction is facilitated by puckering of the four-membered ring. The relatively close approach of the ortho-substituent to the now octahedral phosphorus stabilizes cis TS and increases the ratio of Z-stilbene.49, 50 P-Cl bond interaction will further increase with the second chloro group introduced, resulting in the fact that the ratio of Z-stilbene is higher than that for ochlorobenzaldehyde. Meanwhile, 1,2 interaction is also enhanced when the ortho-position of the yield aryl group is bulkiness cyano group. Even when P-Cl bond interaction exists in trans-TS


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for HWE reaction of o-chlorobenzaldehyde, relatively strong 1,2-interaction causes the higher energy gap between cis TS and trans TS, leading to all E-isomers. QA interaction (Fig. 4-b) is a steric interaction between the quaternary ammonium cation and the benzaldehyde substituent. For TS, the quaternary ammonium cation is located under the plane of P-C-C atoms in the four-member ring of the OPA intermediate. The increasing alkyl chain length in the catalyst causes more “naked” electron cloud and higher steric hindrance and QA interaction is generated. With the combination of P-Cl bond in cis TS, energy gap between trans TS and cis TS intensively decreases, thereby increasing the ratio of cis TS to trans TS. Therefore, it is observed that longer the alkyl chain length of the achiral quaternary ammonium salt is, higher the ratio of Z-stilbene is. 3.5. Reusability of TLPTC system In TLPTC system, the aqueous phase was reused by adding the fresh organic phase and the catalyst. HWE reaction rate had a slight decrease, and the yield, geometric selectivity of the product and the volume of the third phase kept unchanged (Table 2). These findings are attributed to the increase in the concentration of side products. Although rates for side reactions of benzaldehyde and phosphonate in this TLPTC system are much lower than that for HWE reaction, benzoic and phosphnic acid can also be detected in the aqueous phase. These acids can couple with phase-transfer catalyst cation and generated ion-pairs exhibit a low catalytic activity than TBAB and TBA+PO−. As the reaction progress, these ion-pairs also are transformed into TBA+PO−. Although the concentration of these acids in the aqueous phase increases, the final yield of stilbene still is higher than 90% with consecutive runs of the third and aqueous phase. Table 2. Effect of reused time on HWE reaction in TLPTC system.a

Reused

Reused

Yield

E/Zb

The initial reaction rate of stilbene


The volume of

The weight of the aqueous

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Phase

The aqueous phase

The third phase and the aqueous phase

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(mol/L*min-1)

the third phase

phase (g)

>99/1

0.0319

0.80

19.6

91

>99/1

0.0266

0.78

19.5

3

90

>99/1

0.0235

0.75

19.6

4

91

>99/1

0.0201

0.73

19.5

5

90

>99/1

0.0178

0.73

19.6

1

92

>99/1

0.0319

0.80

19.6

2

90

>99/1

0.0241

0.68

19.4

3

89

>99/1

0.0181

0.60

19.4

4

87

>99/1

0.0132

0.51

19.3

5

87

>99/1

0.0105

0.42

19.1

number

(%)

1

92

2

a

5 mmol of phosphonate, 5 mmol of benzaldehyde, 0.3 mmol of TBAB, 20 g of 50% (w/w) NaOH, 15 mL of toluene, 1200 rpm, 45 °C. However, the initial reaction rate, the volume of the third phase and isolated yields intensively decreased when both the aqueous phase and the third phase were reused. Because a portion of the catalyst distributes into the organic phase, the concentration of the catalyst in PTC system sharply decreases. Meanwhile, the concentration of benzoic and phosphnic acid increases. Therefore, the lower isolated yield and less third phase are observed. Furthermore, third phase can accelerate the phase separating speed and reduce the loss of the aqueous phase. In LLPTC system, due to the high viscosity of the aqueous phase, phase separation took a long time and the weight of the separated aqueous phase was less than 18.5 g. However, the loss of the aqueous phase for both reused methods was less than 0.5 g (2.5% to the amount of the aqueous phase), which was much less than that in LLPTC system (1.5 g, 7.5%). 4. CONCLUSIONS


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A hydroxide-initiated TLPTC system for HWE reaction of the “complex” carbanion was developed. The third phase was generated with only 5% equiv of the catalyst to the reactants . TLPTC system afforded relatively high reaction rate, isolated yield and reusability than LLPTC sytem, and was suitable for both “weakly acidic” and “moderately acidic” phosphonates. Products were all E-isomers for HWE reaction, except with benzaldehydes contained orthochloro substitution. The isolated yield could reach to more than 93% with the proper catalyst for benzaldehydes bearing EWGs. Geometric selectivity also depended on the nature of achiral quaternary ammonium salt. The shorter the alkyl chain of quaternary ammonium salt was, the higher the ratio of E-isomer was. 1,2-interaction and QA interaction would influence the transmit state energy of OPA. Isolated yield and geometric selectivity kept unchanged and the weight loss of the aqueous phase was lower than 2.5%, when the aqueous phase was reused. The present research provides a green commercial route for HWE reaction, and new sights on the hydroxideinitiated TLPTC system.

AUTHOR INFORMATION Corresponding Author *(Q. Zhao) Phone: +86-571-86843609; fax: +86-571-86843666; E-mail: [email protected] Notes The authors declare no competing ﬁnancial interest. ACKNOWLEDGMENT One of the authors is thankful to Dr. Guimin Zhang, Shanghai Heliya Fine Chemicals Co., Ltd., for his continual encouragement. This work is supported by Science Foundation of


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Zhejiang Sci-Tech University (ZSTU) under Grant No. 16012058-Y and Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology of Zhejiang Sci-Tech University (CETT 2016001). REFERENCES (1) Wu, H.-S.; Tan, W.-H., Kinetic Study of Carbonylation of α-Bromo-p-xylene with Iron Pentacarbonyl by Phase-Transfer Catalysis. J. Catal. 1998, 178, (2), 604. (2) Starks, C. M.; Liotta, C. L.; Halpern, M., Phase-Transfer Catalysis Reaction with Strong Bases In Phase-Transfer Catalysis: Fundamental, Applications, and Industrial Perspectives, Chapman & Hall: New York, 1994. (3) Makosza, M.; FedoryDski, M., Phase Transfer Catalysis. Cataly Rev 2003, 45, (3), 321. (4) Wu, H.-S.; Lee, C.-S., Catalytic activity of quaternary ammonium poly(methylstyrene-costyrene) resin in an organic solvent/alkaline solution. J. Catal. 2001, 199, (2), 217. (5) Yadav, G. D.; Jadhav, Y. B., Role of the Omega Phase in the Analysis and Intensification of Solid-Liquid Phase-Transfer-Catalyzed Reactions. Langmuir 2002, 18, (16), 5995. (6) Wu, H. S.; Wang, C. S., Liquid-solid-liquid phase-transfer catalysis in sequential phosphazene reaction: kinetic investigation and reactor design. Chem. Eng. Sci. 2003, 58, (15), 3523. (7) Yadav, G. D.; Lande, S. V., Liquid-Liquid-Liquid Phase Transfer Catalysis: A Novel and Green Concept for Selective Reduction of Substituted Nitroaromatics. Adv. Synth. Catal. 2005, 347, (9), 1235. (8) Yadav, G. D.; Badure, O. V., Role of third phase in intensification of reaction rates and selectivity: Phase-transfer catalyzed synthesis of benzyl phenyl ether. Ind. Eng. Chem. Res. 2007, 46, (25), 8448. (9) Gao, B. J.; Zhuang, R. B.; Guo, J. F., Preparation of Polymer-Supported Polyethylene Glycol and Phase-Transfer Catalytic Activity in Benzoate Synthesis. AICHE J. 2010, 56, (3), 729. (10) Baj, S.; Siewniak, A., Tri-liquid system in the synthesis of dialkyl peroxides using tetraalkylammonium salts as phase-transfer catalysts. Appl. Catal., A 2010, 385, (1-2), 208. (11) Yadav, G. D., Insight Into Green Phase Transfer Catalysis. Top. Catal. 2004, 29, (3-4), 145. (12) Tundo, P.; Perosa, A., Multiphasic heterogeneous catalysis mediated by catalyst-philic liquid phases. Chem. Soc. Rev. 2007, 36, (3), 532. (13) Wang, D.-H.; Weng, H.-S., Solvent and salt effects on the formation of third liquid phase and the reaction mechanisms in the phase transfer catalysis system Reaction between N-butyl bromide and sodium phenolate. Chem. Eng. Sci. 1995, 50, (21), 3477. (14) Yadav, G. D.; Desai, N. M., Selectivity engineering of phase transfer catalyzed alkylation of 2'-hydroxyacetophenone: Enhancement in rates and selectivity by creation of a third liquid phase. Org. Process Res. Dev. 2005, 9, (6), 749. (15) Yadav, G. D.; Reddy, C. A., Kinetics of the n-butoxylation of p-chloronitrobenzene under liquid- liquid-liquid phase transfer catalysis. Ind. Eng. Chem. Res. 1999, 38, (6), 2245. (16) Jin, G.; Morgner, H.; Ido, T.; Goto, S., Formation of a Third Liquid Phase and Its Reuse for Dibenzyl Ether Synthesis in a Tetraalkylammonium Salt Phase Transfer Catalytic System. Catal. Lett. 2003, 86, (4), 207.


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(17) Neumann, R.; Sasson, Y., Mechanism of base-catalyzed reactions in phase-transfer systems with poly(ethylene glycols) as catalysts. The isomerization of allylanisole. J. Org. Chem. 1984, 49, (19), 3448. (18) Mason, D.; Magdassi, S.; Sasson, Y., Role of a third liquid phase in phase-transfer catalysis. J. Org. Chem. 1991, 56, (26), 7229. (19) Sowbna, P. R.; Yadav, G. D.; Ramkrishna, D., Population balance modeling and simulation of liquid liquid liquid phase transfer catalyzed synthesis of mandelic acid from benzaldehyde. AICHE J. 2012, 58, (12), 3799. (20) Denmark, S. E.; Weintraub, R. C.; Gould, N. D., Effects of charge separation, effective concentration, and aggregate formation on the phase transfer catalyzed alkylation of phenol. J. Am. Chem. Soc. 2012, 134, (32), 13415. (21) Maryanoff, B. E.; Reitz, A. B., The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects. Chem. Rev. 1989, 89, (4), 863. (22) Gu, Y.; Tian, S. K., Olefination reactions of phosphorus-stabilized carbon nucleophiles. Top Curr Chem 2012, 327, 197. (23) Abell, A. D.; Edmonds, M. K., The wittig and related reaction. In Organophosphorus Reagents: A Practical Approach in Chemistry, Murphy, P. J., Ed. Oxford University Press, : Oxford, UK, 2004; pp 99. (24) Edmonds, M.; Abell, A., The Wittig Reaction. In Modern Carbonyl Olefination, WileyVCH Verlag GmbH & Co. KGaA: 2004; pp 1. (25) Al Jasem, Y.; El-Esawi, R.; Thiemann, T., Wittig- and Horner-Wadsworth-Emmonsolefination reactions with stabilised and semi-stabilised phosphoranes and phosphonates under non-classical conditions. J. Chem. Res. 2014, 38, (8), 453. (26) Pascariu, A.; Ilia, G.; Bora, A.; Iliescu, S.; Popa, A.; Dehelean, G.; Pacureanu, L., Wittig and Wittig-Horner reactions under phase transfer catalysis conditions. Cent. Eur. J. Chem. 2003, 1, 491. (27) Odinets, I. L.; Matveeva, E. V., Ionic Liquids and Water as "Green" Solvents in Organophosphorus Synthesis. Curr. Org. Chem. 2010, 14, (12), 1171. (28) Gu, Y.; Tian, S.-K., Olefination reactions of phosphorus-stabilized carbon nucleophiles. Top. Curr. Chem. 2012, 327, 197. (29) Piechucki, C., Horner reaction in an aqueous two-phase system using phase-transfer catalysis. Synthesis 1974, (12), 869. (30) Sinisterra, J. V.; Fuentes, A.; Marinas, J. M., Barium hydroxide as catalyst in organic reactions. 17. Interfacial solid-liquid Wittig-Horner reaction under sonochemical conditions. J. Org. Chem. 1987, 52, (17), 3875. (31) Mouloungui, Z.; Delmas, M.; Gaset, A., The Wittig-Horner reaction in weakly hydrated solid/liquid media: structure and reactivity of carbanionic species formed from ethyl (diethyl phosphono)acetate by adsorption on solid inorganic bases. J. Org. Chem. 1989, 54, (16), 3936. (32) Dabek, S.; Prosenc, M. H.; Heck, J., Dipolar sesquifulvalene compounds with (tetraaryl-· 4cyclobutadiene)(· 5- cyclopentadienediyl)cobalt(I) complex units as electron donors. Organometallics. 2012, 31, (19), 6911. (33) Popa, A.; Avram, E.; Lisa, G.; Visa, A.; Iliescu, S.; Parvulescu, V.; Ilia, G., Crosslinked polysulfone obtained by Wittig-Horner reaction in biphase system. Polym. Eng. Sci. 2012, 52, (2), 352.


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(34) Zhao, Q.; Sun, J.; Li, J.; He, J., Kinetics and mechanism of Horner Wadsworth Emmons reaction of weakly acidic phosphonate in solid liquid phase-transfer catalysis system. Catal. Commun. 2013, 36, (0), 98. (35) Zhao, Q.; Sun, J.; Liu, B.; He, J., Synthesis of stilbene, 1,4-distyrylbenzene and 4,42 distyrylbiphenyl via Horner Wadsworth Emmons reaction in phase-transfer catalysis system. Dyes. Pigments. 2013, 99, (2), 339. (36) Zhao, Q.; Sun, J.; Liu, B.; He, J., Novel kinetics model for third-liquid phase-transfer catalysis system of the “complex” carbanion: Competitive role between catalytic cycles. Chem. Eng. J. 2015, 280, 782. (37) Winter, A.; Friebe, C.; Hager, M. D.; Schubert, U. S., Synthesis of rigid π-conjugated mono, bis-, tris-, and tetrakis(terpyridine)s: Influence of the degree and pattern of substitution on the photophysical properties. Eur. J. Org. Chem. 2009, 2009, (6), 801. (38) Hahn, B. T.; Tewes, F.; Fröhlich, R.; Glorius, F., Olefin Oxazolines (OlefOx): Highly Modular, Easily Tunable Ligands for Asymmetric Catalysis. Angew. Chem. Int. Ed. 2010, 49, (6), 1143. (39) Lee, L.-W.; Yang, H.-M., Combination of a Dual-Site Phase-Transfer Catalyst and an Ionic Liquid for the Synthesis of Benzyl Salicylate. Ind. Eng. Chem. Res. 2014, 53, (31), 12257. (40) Yadav, G. D.; Badure, O. V., Role of Third Phase in Intensification of Reaction Rates and Selectivity: Phase-Transfer Catalyzed Synthesis of Benzyl Phenyl Ether. Ind. Eng. Chem. Res. 2007, 46, (25), 8448. (41) Yadav, G. D.; Lande, S. V., Intensification of Rates and Selectivity Using Tri-liquid versus Bi-liquid Phase Transfer Catalysis: Insight into Reduction of 4-Nitro-o-xylene with Sodium Sulfide. Ind. Eng. Chem. Res. 2006, 46, (10), 2951. (42) Taha, N.; Sasson, Y.; Chidambaram, M., Phase transfer methodology for the synthesis of substituted stilbenes under Knoevenagel condensation condition. Appl. Catal., A 2008, 350, (2), 217. (43) Thompson, S. K.; Heathcock, C. H., Effect of cation, temperature, and solvent on the stereoselectivity of the Horner-Emmons reaction of trimethyl phosphonoacetate with aldehydes. J. Org. Chem. 1990, 55, (10), 3386. (44) Appel, R.; Loos, R.; Mayr, H., Nucleophilicity Parameters for Phosphoryl-Stabilized Carbanions and Phosphorus Ylides: Implications for Wittig and Related Olefination Reactions. J. Am. Chem. Soc. 2009, 131, (2), 704. (45) Zhao, Q.; Sun, J.; Liu, B.; He, J., Anion exchange cycle of catalyst in liquid–liquid phasetransfer catalysis reaction: Novel autocatalysis. Chem. Eng. J. 2015, 262, 756. (46) Zhao, Q.; Sun, J.; Liu, B.; He, J., Synthesis of stilbene, 1,4-distyrylbenzene and 4,4′distyrylbiphenyl via Horner–Wadsworth–Emmons reaction in phase-transfer catalysis system. Dyes. Pigments. 2013, 99, (2), 339. (47) Entezari, M. H.; Shameli, A. A., Phase-transfer catalysis and ultrasonic waves. I. Cannizzaro reaction. Ultrason. Sonochem. 2000, 7, (4), 169. (48) Byrne, P. A.; Gilheany, D. G., The modern interpretation of the Wittig reaction mechanism. Chem. Soc. Rev. 2013, 42, (16), 6670. (49) Dunne, E. C.; Coyne, Ã. A. J.; Crowley, P. B.; Gilheany, D. G., Co-operative ortho-effects on the Wittig reaction. Interpretation of stereoselectivity in the reaction of ortho-halo-substituted benzaldehydes and benzylidenetriphenylphosphoranes. Tetrahedron Lett. 2002, 43, (13), 2449. (50) Robiette, R.; Richardson, J.; Aggarwal, V. K.; Harvey, J. N., Reactivity and Selectivity in the Wittig Reaction: A Computational Study. J. Am. Chem. Soc. 2006, 128, (7), 2394.


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Third-Liquid Phase Transfer Catalysis for Horner–Wadsworth

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